Rotation-vibration analysis of the Coriolis-coupled ν5g, ν6g, ν8g and ν9 bands of H2CCO

Medium resolution infrared grating spectra of gaseous ketene, H₂CCO were recorded between 1000 and 400 cm^?1, both at instrument temperature (40°C) and with cooling (?40°C). Interferometric Fourier spectra were also measured at ?70°C with resolution 0.22 cm^?1 between 450 and 330 cm^?1. The K structure of the fundamentals ν₅, ν₆, ν₈, and ν₉ was assigned. These fundamentals are coupled by a-axis Coriolis interactions. These couplings were analysed on the symmetric top basis for setting up the perturbation matrix and by utilizing the K-dependent Coriolis shifts of levels. A preliminary analysis of the Coriolis intensity anomalies was also undertaken.Band center values from combination differences are $\text{ν}{}_5{}^0\text{= 587.30 (27)}$ and $\text{ν}{}_6{}^0\text{= 528.36 (39)}\text{cm}{}^{\mathrm{?1}}$. Synthetic spectra indicate the band origins of ν₈ and ν₉ to be close to 977.8 and 439.0 cm^?1, respectively. Estimates of Coriolis coupling constants obtained from synthetic spectra are $\text{ζ}{}_{58}{}^{\mathrm{a}}\text{= + 0.33 (5)}$, $\text{ζ}{}_{68}{}^{\mathrm{a}}\text{= + 0.714 (20)}$, $\text{ζ}{}_{59}{}^{\mathrm{a}}\text{= ? 0.774 (20)}$, and $\text{ζ}{}_{69}{}^{\mathrm{a}}\text{= ? 0.30 (2)}$. Approximate ratios of unperturbed vibrational transition moments obtained from spectral simulations are $\text{M}{}_8{}^0\text{:±iM}{}_5{}^0\text{:±iM}{}_6{}^0\text{:M}{}_9{}^0\text{≈ +2:?9:+10:+0.5}$.